Copper and zinc alkyl trithiocarbonates and mercaptides as bird repellents



United States Patent 3,171,780 COPPER AND ZINC ALKYL TRITHIOCAR- BONATES AND MERCAPTIDES AS BIRD REPELLENTS Tyson H. Mullen, Bartlesvllle, Okla assignor to Phillips Petroleum Company, a corporation of Delaware No Drawing. Filed June 7, 1960, Ser. No. 34,372 24 Claims. (Cl. 167-46) This invention relates to a method of repelling birds. In one of its aspects, the invention relates to a method for rendering a locus repellent to birds. In another of its aspects, the invention relates to a method for rendering a surface repellent to birds. In still another of its aspects, the invention relates to a method for treating seeds, grain, and the like so as to render the same repellent to birds that normally feed thereon. A further aspect of the invention relates to a method for treating buildings to render the same repellent to birds.

A number of repellents for certain pests, such as insects and rodents have been developed and are known in the art. However, very little success has been attained in the search for a material which is repellent to birds. It is very desirable to be able to repel birds from certain areas and surfaces. For instance, the loss of grain at the present time to feeding birds represents a large financial loss to the farmers of this country each year. Also, as is well known, many birds through their roosting habits foul buildings, sidewalks and the like.

It is an object of this invention to provide new bird repellent compositions. It is a further object of this invention to provide a method for repelling birds. Still another object is to provide a method for rendering surfaces repellent to birds.

Other aspect, objects, and the several advantages of the invention are apparent from a study of the disclosure and the appended claims.

According to the present invention, it has been discovered that birds can be repelled from surfaces frequented by them by applying to said surfaces an amount of at least one compound selected from the groups consisting of wherein R is an alkyl group having from 1 to carbon atoms, M is a metal ion selected from the group consisting of cuprous and zinc, and n is the valence of the metal ion;

S (R-S-PJ-S) uM wherein R is an alkyl group containing from 1 to 20 carbon atoms, M is a metal ion selected from the group consisting of cupric and zinc, and n is the valence of the metal ion;

Cupric trithiocarbonate;

Zinc trithiocarbonate;

Cuprous alkyl sulfonium cyanide;

Zinc alkyl sulfonium cyanide;

Cuprous alkyl sulfonium chloride;

Zinc alkyl sulfonium chloride;

2,5-dithiahexane-cuprous cyanide adduct; 2,5-dithiahexane-zinc cyanide adduct; 2,5-dithiahexane-cuprous chloride adduct; and 2,5-dithiahexane-zinc chloride adduct.

ice

The alkyl group of the sulfonium compounds conta from 1 to 20 carbon atoms.

Specific examples of compounds falling within the set of the above are:

Cuprous methyl mercaptide Cuprous n-octyl mercaptide Cuprous tert-butyl mercaptide Cuprous tert-octyl mercaptide Cuprous tert-dodecyl mercaptide Zinc methyl mercaptide Zinc n-octyl mercaptide Zinc tert-butyl mercaptide Zinc tert-octyl mercaptide Zinc tert-dodecyl mercaptide Cupric methyl trithiocarbonate Cupric tert-butyl trithiocarbonate Cupric tert-dodecyl trithiocarbonate Zinc trithiocarbonate Zinc methyl trithiocarbonate Zinc tert-butyl trithiocarbonate Zinc tent-dodecyl trithiocarbonate Cuprous n-butyl sulfonium cyanide Zinc n-butyl sulfonium cyanide Cuprous tert-butyl sulfonium chloride Zinc tert-butyl sulfonium chloride 2,5-dithiahexane-cuprous cyanide adduct 2,5-dithiahexane-zinc cyanide adduct 2,5-dithiahexane-cuprous chloride adduct 2,5-dithiahexane-zinc chloride adduct and the like.

The bird repellents of this invention can be applied their intended purpose as the pure compound, or in co bination with a carrier or inert materials such as SOlllilt or emulsions. Solvents or carriers can be used which a substantially inert with respect to the active bird rep lent. Examples of carrier materials which can be e ployed are Acetone Deodorized kerosene Naphthas Isoparafiinic hydrocarbon fractions boiling in the proximate range of 260800 F. (Soltrol) and the like. If desired, the bird repellents of this vention can be applied as aqueous emulsions, in wh case, a suitable emulsifying or wetting agent is employ The repellent materials can also be applied as dusts, usi such solid carriers as kieselguhr and the like. In ad tion, the materials for repelling birds can be applied surfaces from which it is desired to repel these anim in conjunction with an adhesive.

The bird repellents of this invention can be applied the above-described form by spraying, brushing, dusti1 etc. The preferred method of application is by sprayi a liquid composition on the surface to be treated. Wh applying the repellents of this invention in a solvent carrier, the liquid compositions will normally cont: from 0.1 to 10 weight percent of one of the above-t scribed compounds, although concentrations above a below this range can be used. When these materials 2 applied in the form of dusts, the concentration of acti ingredient is preferably within the range between 1 a 20 weight percent, although concentrations above a below this range are applicable.

The bird repellents of this invention are applied to st faces in a manner so as to deposit an amount within t Table I-Continued TEST COMPOUND: cUPRoUs N-BUTYL BULFONIUM CYANIDE Test Oom- Run pound Comparative Per- Grams No. Compound cent 'laken Bird Per- Grams cent Taken 1 10 12 Dove.

1 2 10 U Pigeon.

1 0 l0 0 Dove.

1 15 10 0 Pigeon.

1 2 10 0 Blackbird.

TEST COMPO UND: 2,5-DITHIAHEXANE-C UP ROUS CYANIDE ADDUCT 203.-.. 10 0 None 10 48 Pigeon. 204- 10 0 Anthraquiuone 10 5 Dove. 205.. 0 Arasan 50 10 0 Pigeon. 206--.- 10 0 Arasan 75 10 0 Do. 207. 4 0 Anthraquinone 10 0 Do. 208.... 4 1 Arasan 50.-. 10 0 Do. 209. 2 0 Anthraquino 10 0 Do. 210-... 2 6 Arasan 50... 10 0 Do. 211. 1 6 Anthraquinone 10 0 Do. 212-.-. l 0 Arasan 60 10 0 Do.

TEST OOMPO UND: 2,5-DI'IHIAHEXANE-ZINC CHLO RIDE .ADD UC'I 213. 10 2 None 10 50 Pigeon. 214. 10 0 Spergon 10 8 Do. 215. 1O 0 Quinizarine 10 0 Dove. 216. 10 0 1 Pigeon. 217.--. 10 0 0 Dove. 218-.-. 4 10 0 Pigeon. 219- 4 0 0 Do. 220. 2 2 0 D0. 221..-- 2 0 Arasan 50 10 0 Do. 222. 1 0 Anthraquinone...- 10 0 Do. 223.... 1 0 Arasan 50 l0 0 Do. 224. 1 0 Spergon 10 0 Ygllog- Tetrachloro-para-benzoquinone, produced by U.S. Rubber Corpora- 1 Tetramethyl thiuram disulfide, produced by Du Pont.

EXAMPLE II In another test, 3.4 grams of several test compounds were dissolved or dispersed in 20 mls. of xylene. The resulting solution or dispersion was mixed with 340 grams (500 mls.) of grain. The xylene was subsequently allowed to evaporate. Separate pans containing the test grains and a control sample were placed on a building roof for a period of 10 days or until all of the grain had In this outdoor test, all compounds showed some repellency toward birds. The mercaptides were particularly attractive.

Reasonable variation and modification are possible within the scope of the foregoing disclosure and the appended claims to the invention, the essence of which is that it has been found that birds can be repelled by applying to the surfaces frequented by them an amount of at least one of the compounds selected from the group consisting of cuprous and zinc alkyl sulfonium chlorides, cuprous and zinc alkyl sulfonium cyanides, dithiahexane 'adducts with cuprous and zinc chlorides and cuprous and zinc cyanides, cuprous and zinc mercaptides, and zinc a cupric trithiocarbonates.

I claim:

1. A method of repelling birds from a material whi otherwise a bird would eat comprising treating said ma rial with at least one compound of the formula wherein R is an alkyl group having from 1 to 20 carb atoms.

2. A material protected against ravaging or eating birds, said material having been impregnated according the method of claim 1.

3. A method of repelling birds from a material whi otherwise a bird would eat comprising treating said ma rial with at least one compound of the formula S (R-S- i-S) nM wherein R is an alkyl group containing from 1 to carbon atoms, M is a metal ion selected from the gro consisting of cupric and zinc, and n is the valence of 1 metal ion.

4. A material protected against ravaging or eating birds, said material having been impregnated accordi to the method of claim 3.

5. A method of repelling birds from a material whi otherwise a bird would eat comprising treating said ma rial with cupric trithiocarbonate.

6. A material protected against ravaging or eating birds, said material having been impregnated accordi to the method of claim 5.

7. A method of repelling birds from a material whi otherwise a bird would eat comprising treating said ma rial with zinc trithiocarbonate.

8. A material protected against ravaging or eating birds, said material having been impregnated according the method of claim 7.

9. A method of repelling birds from a material whi otherwise a bird would eat comprising treating said ma rial with a cuprous alkyl sulfonium cyanide, wherein t alkyl group contains from 1 to 20 carbon atoms.

10. A material protected against ravaging or eati by birds, said material having been impregnated acco1 ing to the method of claim 9.

11. A method of repelling birds from a material whi otherwise a bird would eat comprising treating said ma rial with a zinc alkyl sulfonium cyanide, wherein the all group contains from 1 to 20 carbon atoms.

12. A material protected against ravaging or eating birds, said material having been impregnated accordi to the method of claim 11.

13. A method of repelling birds from a material whi otherwise a bird would eat comprising treating said ma rial with a cuprous alkyl sulfonium chloride, wherein t alkyl group contains from 1 to 20 carbon atoms.

14. A material protected against ravaging or eating birds, said material having been impregnated accordi to the method of claim 13.

15. A method of repelling birds from a material whi otherwise a bird would eat comprising treating said ma rial with a zinc alkyl sulfonium chloride, wherein t alkyl group contains from 1 to 20 carbon atoms.

16. A material protected against ravaging or eating birds, said material having been impregnated accordi to the method of claim 15.

17. A method of repelling birds from a material whi otherwise a bird would eat comprising treating said mat rial with 2,5-dithiahexane-cuprous cyanide adduct.

18. A material protected against ravaging or eating birds, said material having been impregnated accordi to the method of claim 17.

19. A method of repelling birds from a material whi otherwise a bird would eat comprising treating said mat rial with 2,5-dithiahexane-zinc cyanide adduct.

7 8 0. A material protected against ravaging or eating by otherwise a bird would eat comprising treating said matels, said material having been impregnated according rial with 2,5-dithiahexane-zinc chloride adduct. he method of claim 19. 24. A material protected against ravaging or eating by 1. A method of repelling birds from a material which birds, said material having been impregnated according :rwise a bird would eat comprising treating said mate- 5 to the method of claim 23.

with 2,5-dithiahexane-cuprous chloride adduct. 2. A material protected against ravaging or eating by References Cited m the file of thls Patent ls, said material having been impregnated according UNITED STATES PATENTS he method of claim 21. 2,779,703 1 Crouch et a1. Jan. 29, 1957 3. A method of repelling birds from a material which 1 2,840,502 Lambreck June 24, 1958 

1. A METHOD OF REPELLING BIRDS FROM A MATERIAL WHICH OTHERWISE A BIRD WOULD EAT COMPRISING TREATING SAID MATERIAL WITH AT LEAST ONE COMPOUND OF THE FORMULA 